Monazo dyes and their metal complexes

ABSTRACT

MONOAZO DYES, THEIR METAL COMPLEXES AND THEIR METAL MIXED COMPLEXES WITH OTHER METALLIZABLE DYES, WHICH IN THE METAL FREE FORM HAVE THE FORMULA   1-((2-(HO-),4-(HO3S-),6-X-NAPHTHYL)-N=N-),2-(A-NH-)   NAPHTHALENE   WHERE X STANDS FOR A HYDROGEN ATOM OR THE NITRO GROUP AND A FOR AN ARYL RADICAL WHICH MAY BEAR FURTHER SUBSTITUENTS.

United States Patent 3,632,568 MONAZO DYES AND THEIR METAL COMPLEXESReinhard Neier, Basel, Switzerland, asslgnor to Sandoz Ltd. (also knownas Sandoz A.G.), Basel, Switzerland No Drawing. Filed Mar. 4, 1968, Ser.No. 709,878

Claims priority, applicagign Szvtzerland, Mar. 8, 1967,

Int. Cl. cosd 45/20,- D0611 1/02 US. Cl. 260-145 6 Claims ABSTRACT OFTHE DISCLOSURE Monoazo dyes, their metal complexes and their metal mixedcomplexes with other metallizable dyes, which in the metal free formhave the formula NH-A where X stands for a hydrogen atom or the nitrogroup and A for an aryl radical Which may bear further substituents.

This invention relates to new monoazo dyes and their metal complexes,which in the metal free form have the formula l H O 3S8 N:N

Where X stands for a hydrogen atom or the nitro group and A for an arylradical, preferably a phenyl radical, which may bear furthersubstituents.

These dyes can be produced by coupling 1 mole of the diazo compound ofan amine of formula IfH-A The azo dyes of Formula I can be metallized insub stance or on the fibre. They can be treated with a metal yieldingagent under conditions giving rise to a metalcontaining azo dye whichcontains essentially one metal atom in complex combination with onemolecule of the azo compound. For the production of these 1:1 metalcomplex compounds it is preferable to use an agent which donateschromium or cobalt.

The new azo dyes can alternatively be treated with a metal yieldingagent in such a way as to form metal-containing azo dyes bearingessentially one metal atom in complex combination with two molecules ofthe azo compound. For the production of these 1:2 metal complexcompounds it is preferable to allow an amount of a metal ice yieldingagent, for example a chromium or cobalt donor, containing at least onemole but less than two moles of metal to act upon two moles of the azocompound.

The metallizing reaction is conducted to best advantage in an alkalineaqueous or organic medium, to which the metal compound is added in thepresence of a compound which maintains the metal dissolved in complexcombination in caustic alkaline medium, for example tartaric, citric orlactic acid.

Examples of suitable chromium compounds are chromic fluoride, chromicsulphate, chromic formate, chromic acetate, chromic potassium sulphateand chromic ammonium sulphate. The chromates, e.g sodium and potassiumchromate and bichromate, are also highly suitable.

Suitable cobalt compounds include cobalt formate, cobaltous acetate andcobalt sulphate.

The metal free or metal containing compounds obtained by the reactionare precipitated from the aqueous medium, preferably by the addition ofsalt, and are then filtered off, washed and dried.

The metallization of a mixture of a dye of Formula I, if desired in theform of its metal complex, and a second metallizable dye different fromit, preferably another metallizable azo dye, for example a monoazo ordisazo type, results in valuable mixed metal complex dyes, the hue anddyeing properties of which can be brought closely into line withrequirements for any prospective sector of use by an appropriateselection of starting compounds.

Dyes of the aforestated types are to be found, for example, in thebenzene-azobenzene, benzene-azonaphthalene, benzene-azopyrazolone,benzene azoaminopyrazol, benzene-azoacetoacetylaminobenzene and benzeneazobarbituric acid series. It is preferable for these dyes to conform tothe general formula (IIIa) where K stands for the radical of a couplingcomponent of the benzene, naphthalene, pyrazolone,acetoacetylaminobenzene or barbituric acid series,

V and Y each stands for identical or different substituents capable ofmetal complex formation,

Y is in the ortho position to the N=N-group,

OH; (IV) where D stands for a hydrocarbon radical which may bear furthersubstituents and the ring B may likewise be further substituted.

A particular good mixed cobalt complex dye is obtained by reacting witha cobalt yielding agent a mixture of two monoazo compounds of formulaeThe radical A in Formula I may be substituted by halogen, such aschlorine or bromine, or by an alkyl or alkoxy radical which may itselfbe substituted. In

each instance the alkyl or alkoxy radicals bear 1 to 8 or preferably 1to 4 carbon atoms.

The radical D in Formula IV may be an unsubstituted alkyl radical, butit represents preferably, a phenyl or naphthyl radical, substituted orunsubstituted as desired. The substituents which these radicals may bearinclude the sulphonic acid and carboxylic acid groups, the nitro, cyano,hydroxyl and trifiuoromethyl groups, halogen atoms, such as chlorine orbromine atoms, alkyl or alkoxy groups which may be further substituted,the sulphonic acid amide and carboxylic acid amide groups, alkylsulphonyl and arylsulphonyl.

The unmetallized azo dyes obtained in the present process are suitablefor the dyeing and printing of natural and synthetic polyamide fibresand of paper and leather.

The dyeings on these materials are metallized in the dyeing medium or ina fresh bath, on which. they show good light and wet fastnessproperties.

The homogeneous or mixed metal containing dyes are suitable for theexhaustion dyeing, pad dyeing and printing of animal fibres andsynthetic polyamide fibres. The mixed metal containing dyes areparticularly suitable for leather dyeing. Given sufficiently goodsolubility in organic solvents, they can be employed further for themass coloration of fibres in the spinning solution and and is described,which among other uses is employed for wool dyeing, It is surprisingthat the mixed cobalt and chromium complexes of a monoazo dye of Formula1 and a dye different from this show better fastness to washing andmilling on wool than the aforestated dye of this patent.

The new dyes are highly suitable for dyeing various types of leathersince they have very good afiinity and give level dyeings withoutvariations of shade. They show very little sensitivity to hard water,level put excellently and have good light fastness. They have goodfastness to washing, bufiing, acids, alkalis and perspiration, are fastto migration and are not affected by formaldehyde.

On natural and synthetic polyamides, such as wool and nylon, they havevery good neutral aifinity and power of build-up. The fastness towashing, water, sea water, perspiration, milling, alkali, acids,chlorine, carbonizing, peroxide, cross dyeing, rubbing, pressing anddecatizing is excellent. The sensitivity to metals is minimal, thefastness to formaldehyde and repeated washing, good. They are used withadvantage where high end use colour fastness is required.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

EXAMPIJE 1 28.4 parts of diazotized1-amino-2-hydroxy-6-nitronaphthalene-4-sulphonic acid are entered into asolution of 21.9 parts of Z-phenylaminonaphthalene in 200 parts ofisopropyl alcohol. After the addition of 15 parts of concentratedhydrochloric acid and 50 parts of water the mixture is raised to 60 andstirred until the coupling reaction is complete. Water is added toprecipitate the dye, which is then isolated and dried. It is obtained asa dark powder which dissolves in sodium hydroxide solution with apurplish brown colour. It can be applied to wool and subsequentlytreated with a cobalt salt to give an olive green dyeing.

The yield is 90%. If the coupling reaction is carried out withoutisopropyl alcohol, i.e. according to the usual procedure in water in thepresence of acetone or glacial acetic acid, the yield is not higher than50%.

For the production of the cobalt complex in substance 25.7 parts of themonoazo dye obtained as in the foregoing and 5 parts of sodium hydroxideare stirred into 500 parts of water at 70, with the subsequent additionof a solution of 7 parts of cobalt sulphate (CoSOg-5H O) and 1.8 partsof tartatric acid in 50 parts of Water and of 8 parts of 30% sodiumhydroxide solution. These later additions give rise to a viscoussolution of deep blue colour. It is stirred at 70-80 until theunmetallized starting dye has disappeared, upon which 50 parts of sodiumchloride are added. The dye is isolated, dried and ground to give a darkpowder which dissolves in water with an olive colour. On wool, leatherand nylon it gives dyeings of olive shade which show excellent water,perspiration and milling fastness.

EXAMPIJE 2 10.3 parts of the monoazo compound obtained by couplingdiazotized l-amino-Z-hydroxy-6-nitronaphthalene-4-sulphonic acid with2-phenylaminonaphthalene and 6.8 parts of the monoazo compound obtainedby coupling diazotized Z-amino-rl-hydroxy-4-nitrobenzene with 1-phenyl-3-methyl-5-pyrazolone are dissolved with 8 parts of sodiumhydroxide in 300 parts of water at A- solu tion of 5.6 parts ofcrystallized cobaltous sulphate and 1.5 parts of tartaric acid in 80parts of water is added thereto and the reaction mixture is then stirredat 80 until no further traces of the metal free starting compounds areindicated. The reaction product is salted out with sodium chloride,filtered off, dried and ground. It is ob- TABLE A tained as a darkpowder which dissolves in water with an I H III IV oli ve colour and canbe dyed n Wool, silk, leather and synthetic polyamide fibers to givedyeings of oliver shade Example ih g i egog with excellent washmg,milling and perspiration fastness. number Diazo component Am componentMetal wool E AMP 3 4 l-amlno-Z-hy- 2-phenylamino- Cr Green-grey.

, droxy-fi-nitronaphthalene. 103 parts of the monoazo compound obtainedby counaphthalene pling diazotized1-amino-Z-hydroxy-6-nitronaphthalene-4- 5 00 Olive. sulphonic acid with2 phenylaminonaphthalene and 7.8 10 phenylaminoparts of the monoazocompound obtained by coupling d1- 6 do a? Go azotizedZ-amino-1-hydroxy-4-nitrobenzene with l-acetylphefiylallninonap tha ene.amino 7 hydr oxynaphthalene are entered into 100 parts of 7 2phenylamino 00 formamide with the further addit1on of 10 parts ofChIOIIllC droxy-naphthalnaphthalene. ammonium sulphate. The reactionmixture is raised to g i d-a sulphomc 110 and held at this temperaturefor several hours until 8 l-aimino-g-hy- 2-(4-metlhoxy)- C0 D0.

roxy- -nitropheny aminotests give no further indicauon of theunmetallized start naphthalene 4 naphthalene mg compounds. The mixtureis then diluted with 300 parts sulphonic acid. of water and 60 parts ofsodium chloride, upon which the product settles out. It is filtered offand purified by dis- EXAMPLE 9 l t m W g Wlth the 1 2 E12 g i g 9.6parts of the diazo compound obtained by coupling clpltatlon common Satra 3 an 15 SH diazotized 3-amino-4-hydroxy-l,l'-azobenzene with 1-quenfly druid i f It 15 then gbtamfed as a flark phenyl-3-methyl 5pyrazolone 4' sulphonic acid are Powder which dlssolves In Water to iOhve .solutlons; stirred into 70 parts of ethylene glycol with thesubsef l lf' sllk 1e,ather g synthetlc if i i f fibretse quent additionof 10 parts of chromic ammonium sul- 1t l 0 g yemigs owmg exce en asness 0 phate. The mixture is raised to 130 and held at this temfi an i fl h t d perature until the metal-free dye is no longer indicated. e 0llmrts 0 main: 2 31 use The mixture is allowed to cool to 100 and atthis temt i e rep ace q equwla en q perature 10.3 parts of the monoazocompound obtained of atousl l g by coupling diazotized1-amino-2-hydroxy-6-nitronaphcoba g ex 1S 0 tame w 10 gwes yemgs 0thalene-4-sulphonic acid with 2-phenylaminonaphthalene grey s a a Woo Ad f f th t t are added in solution in 30 parts of formamide. The mix-The f0 1 Ta glves etal s 0 er S ar ture is stirred at 100 until there isno further indicalng dyes Whlch are sultable for the Productlon of homo"tion of the metal-free starting dye, on which it is diluted geneous azodyes In accordance Wlth Primedre of with Water and sodium chloride addedto precipitate the EXample Column Speclfies the (halo component,product. On isolation this is purified by dissolving in Column 11 thecouplmg Component, Column 111 the aqueous sodium hydroxide solution,precipitation with metal used for metal complex formation and Column IVcommon salt and filtration. On drying and grinding it is the shade ofthe dyeing on wool. obtained as a dark powder which dissolves in waterwith TABLE B Example number I II III IV V VI 10 10.31-amino-2-hydroxy-6-nitronaphthalenel sulphouic 10.82-amino-l-hydroxybenzene-4-su1phonic acid-2 O0 Grey-green. acid2-phenylarninonaphthalene. tgrlioxyphenylamide Z-phenylaminonapha ene.11 10.3 do 7 2-amino-l-hydroxy-4,6-dinitrobenzeue 2- 00 Olive.

aminonaphthalene. 12 10.3 do 7.2 2-amino-1-hydroXy-4,rdich10robenzene 1-00 Brown.

phenyl-3-methyl-5-pyrazolone. 13 15.4 do 3.1 2-amin-l-hydroxy-fi-nitrobenzene Z-hydroxy- {00 Grey.

naphthalene. Cr Grey-blue. 14 10.3 do 8.42-amino-1-hydroxy-4-nitrobenzene 1-(4- O0 Olive-brown.

snlpho)-phenyl-3-methyl-S-pyrazolone. 15 10.3 do 7.62-amino-l-hydroxybcnzene-4-sulphonic acida- 00 Olive.

mide acetoacetylaminobenzene. 16 10.3 .do 5.62-arninqg-hydroxy-4-chlorobenzene barbitn- Go Do.

no aci 17 10.3 do 7 2-amino-1-hydroxy-4,fidinitrobenzenc 2- C0Olive-brown.

hydroxynaphthalene. 13 do 6.82-arnino4-hydroxy-1,1-azobcnzene-4-sulpl1onic 00 Brown.

acid Z-hydroxynaphthalene. Cr Grey.l-amino-2-hydroxy-6-nitronapthaleneA-sulphonic 7.22-amino-1-hydroxy-4-nitrobenzene l-hydroxy- Co Brown.

acid 2-phenylaminonaphthalene. 4 methylbenzene.l-amino-2-hydroxynaphthalenel-sulphonic acid 7.6Z-amino-1-hydr0xy-4-nitr0benzene 2-phenyl- G0 Olive-green.

Z-phenylaminonaphthalene. aminonaphthalene.l-amino-Z-hydroxy-fi-nitronaphthalene i-sulphonic 7.6Z-amino-1-hydroxy-4,6-dinitrobenzene 1- 00 Brown.

acid 2-phenylaminonaphthalene. phenyl-3-methyl-5-pyrazolone.

2-amin0-1-hydroxy-4-nitrobenzene Z-phenyl- Co Olive-green.

aminonaphthalene. Olive-blue. 2-amino-1-hydroxy-4-nitrobenzeneZ-hydroxy- 00 Grey.

naphthalene. Z-amino-l-hydroxybenzene-l-sulphonic acid- 00 Brown.

phenylamide Z-hydroxynaphthalene. 2-amino-1-hydroxy-4-nitrobenzene1-pheny1-3- Or Do.

methyl-fi-pyrazolone. l-aminobenzene-2-carboxylic acid 1-pheny1-3- CrOlive.

methy1-5-pyrazo1one. 27 10.3l-amino-2-hydroxy-fi-nitronaphthalenel-sulionic 7.42-amino-1-hydroxy-4-nitrobenzene l-(3-chloro)- Co Olive-brown.

acid 2-phenylaminonaphthalene. pheuyl-3-methyl-5-pyrazolone. 28 10.3l-amino-Z-hydroxy-S-nitronaphthalene--sulfonic 8.42-amino-1-hydroxy-knitrobenzene-fi-snlphonic C0 D0. acid2-phenylaminonaphthalene. acid 1-phenyl-3-methyl-5-pyrazolone. Cr Brown.29 10.5 l-amino-Z-hydroxy-fi-nitronaphthalene 4-sulphon1c 6.82-amino-1-hydroxyl nitrobenzene 1-phenyl-3- O0 Olive-brown.

acid 2(3-chloro)-phenylaminonaphthalene. methyl-5-pyrazolone. 30 10.41-amino-2-hydr0xy-6nitronaphthaleneA-sulphonic 6.8 .do C0 D0.

acid 2-(4=-methy1)-phenylaminonaphthalene. 31 10.51-amino-2hydroxy-6-nitronaphthalene--sulphonic 72-ami110-1-hydroxy-4-nitrobenzene 1(3-chloro)- C0 D0,

acid 2-(ethoxy)-phenylaminonaphthalene. phenyl-3-methyl-5-pyrazolone. 3210.3 l-amino-2-hydroxy-fi-nitronaphthalene-l sulphonic 7.02-amino-1-hydr0xy-4,6-d.initrobenzene 2 C0 D acid2-pheny1aminonaphthalene.

hydIoxy-l-naphthaldehyde.

Dyeing Example A One part of the dye obtained as detailed in Example 2is dissolved in 4000 parts of water at 40-50. After previous wettingout, 100 parts of a wool fabric are entered 1 into this dyebath, andafter 2 parts of glacial acetic acid has been dropped in the bath israised to 100 in 30 minutes and held at the boil for one hour. The dyedwool is then removed from the bath, rinsed with Water and dried. Anolive brown dyeing with excellent light, washing and milling fastness isobtained.

A dyeing with similar properties is obtained when the 100 parts of woolare replaced by 100 parts of nylon.

Dyeing Example B 100 parts of freshly tanned, neutralized chrome grainleather are drummed for 30 minutes at 65 in a bath of 250 parts of Watercontaining 1 part of the dye of Example 2. At this point 2 parts of ananionic fatliquor on a sulphonated train oil basis are added anddrumming continued for 30 minutes. The leather is dried and finished inthe normal way. A very level olive brown dyeing is obtained.

The mixed metal containing dyes have good build-up on leather ofdilferent qualities from neutral to weakly 3 acid dyebath, show verygood leathering properties on these leathers, and give dyeings ofconsistent shade having good fastness to bufi'ing, migration, washing,water, perspiration, formaldehyde, pressing and light.

Formulae of representative dyes of the foregoing examples are asfollows:

EXAMPLE 1 The 1:2-cobalt complex of the azo compound of the formula OH IHa gai- EXAMPLE 2 The 1:2-cobalt mixed complex of 10.3 parts of the azocompound of the formula OH I magma No: and 6.8 parts of the azo compoundof the formula Q H0-0N g I -H=N- N ll it I 8 EXAMPLE 12 The 1:2-cobaltmixed complex of 10.3 parts of the azo compound of the formula N0, and7.2 parts of the azo compound of the formula OH I "i -N=NO N I OH;

l Cl

EXAMPLE 21 The 1:2-cobalt mixed complex of 10.3 parts of the azocompound of the formula and 7.6 parts of the azo compound of the formulaOH I -WQ EXAMPLE 25 The 1:2-chromium mixed complex of 10.3 parts of azocompound of the formula and 6.8 parts of the azo compound of the formula0 (in, to,

Having thus disclosed the invention what [I claim is: 1. Monoazo dyewhich, in metal-free form, is of the formula I H0358N=N wherein X is ahydrogen atom or nitro; and

NEE-A 10 A is a member selected from the group consisting of 12. The1:2-cobalt complex according to claim 1 of phenyl, chlorophenyl,bromopheuyl, alkylphenyl the azo compound of the formula andalkoxyphenyl, each alkyl and each alkoxy having from 1 to 4 carbonatoms. NH@

2. A 1:1-metal complex compound of dye according 5 to claim 1. HC:S

3. A 1:2-metal complex compound of dye according to claim 1.

4. A cobalt complex compound of dye according to I claim 1. N02

5. A chromium complex compound of dye according to claim 1. 0 13. The1:2-cobalt mixed complex according to claim MOIlOaZO y accordlllg toclaim 1 Whereln halo 1 of 10.3 parts of the azo compound of the formulaphenyl is chlorophenyl.

7. A complex compound according to claim 2 wherein the metal is a memberselected from the group consisting of chromium and cobalt, I l 8. Acomplex compound according to claim 3 wheres in the metal is a memberselected from the group consisting of chromium and cobalt.

9. A metal complex compound of a mixture of mono- I azo dye according toclaim 1 and a monoazo compound N0;

of the formula and 6.8 parts of the azo compound of the formula I H0 0 ND N-N- i l I OH I HO-C-N N=NC N (Em wherein 6H3 D is a member selectedfrom the group consisting of 1|):

a hydrocarbon radical and a substituted hydrocarbon radical; thehydrocarbon radical is a member The lzzcobalt mixed complex according toclaim selected from the group consisting of alkyl, phenyl 1 of 103 artsof th azo com 0 nd of th f0 U1 and naphthyl; and any substituent on thesubstituted P e p u e rm a hydrocarbon radical is a member selected fromthe group consisting of sulphonic acid, carboxylic acid, H-O nitro,cyano, hydroxy, trifluoromethyl, chlorine,

I bromine alkyl, alkoxy and alkylsulphonyl; each alkyl HO3S and eachalkoxy having from 1 to 4 carbon atoms. 40 10. A 1:2 chromium or 1:2cobalt complex compound of a mixture of (a) monoazo dye according toclaim 1 and (b) monoazo dye of the formula OH HO(fi-I IID and 7.2 partsof the azo compound of the formula N=N-O\ /N 0H t ar-r6 CH3 o1- N=NO\ yNwherein H D is a member selected from the group consisting of C 3phenyl, chlorophenyl and sulfophenyl and ring B 01 is eitherunsubstituted or substituted, any substituent P g amember selected fromthe group t- 1s. The 1:2-cobalt mixed complex according to claim 0fmtro, azobenlene and chlOrO- 1 of 10.3 parts of the azo compound of theformula 11. A cobalt complex compound according to claim 1 of a mixtureof two monoazo compounds of the formulae O OH NH (1)11 T O E038 N=Nnoas- N=N rim, I 1 10,,

and 7.6 parts of the azo compound of the formula and 1 H0 0 NO OH HOC--N O u I] F 16. The 1:2-chromium mixed complex according to ReferencesCited claim 1 of 10.3 parts of the azo compound of the formula UNITEDSTATES PATENTS 2,824,864 2/1958 Buehler 260145 5 3,516,980 6/1970 Doreet a1 260- 145 HOBS- FOREIGN PATENTS 1,352,623 1/1964 France 260-145 10CHARLES B. PARKER, Primary Examiner and 6.8 parts of the azo compound ofthe formula D- M- PAP UGA: Assistant Examiner 3 C us. 01. X.R.

l; 260-37 NP, 147, 149, 150, 151, 160, 163, 176, 194,

UNITED STATES PATENT @FFKIE QEBTIFICATE r ECU Patent No. 3 Dated January4, 1972 Inventofli) REINHARD NEIER It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 20, (after the formula) insert a comma line 59, "I"should read -(I)-. Column 2, line 21, "I," should read -(I),--; line 53,"group" should read group;; line 54, "ethoxy" should read ethoxy;-; line60, "I" should read (I); line 67, (after the formula) "(IV)" should read(IV),. Column 3, line 1, "particular" should read particularly-; line 8,(in the formula) should read line 22, "I" should read (I)--- line 27,"IV" should read (IV)--; line 28, "represents" should read-represents,-; line 51, "I" should read (I)-;

line 66, (in the formula) "N0 should read N0 line 75, (in the formula)"N0 should read NO Column 4, line 3, "I" should read (I)-;

line 50, "tartatric" should read tartaric-. Column 7, line 35,

"leathering" should read --leveling-. Column 8, *line 29 (in theformula) "H0 8" should read -HO S; line 37, (in the formula) should readline 43, "parts of" should read parts of the-. Claim 1, (after 9 0 N1the formula) insert a comma Claim 9 (after the formula) insert a commaClaim 10, (after; the formula) insert a comma Claim 13,

(in the first formula) "N0 should read N0 (in the second formula) "N0should read NO Signed and sealed this 6th day of March 1973.

(SEAL) Attest: 4

EDWARD M. FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents FORM PO-105O (10459) uscoMM-Dc 60376-1 69 9 U.S. GO ERNMENTPRINHNG OFFICE: I969 0-366-334

